TWI232860B - Integrated process for the preparation of epoxides from olefins - Google Patents

Abstract

The invention relates to an integrated process for the preparation of epoxidised ole-fins. In the first stage, dilute hydrogen peroxide solutions are prepared from the elements hydrogen and oxygen and reacted in a subsequent liquid-phase epoxidation with olefin in the presence of titanium silicalite to form epoxidised olefins, and the solvents are returned to the H2O2 process again.

Description

1232860 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (ί) The present invention is a complete method for preparing epoxidized olefins. In the first I1 white segment, the dilute hydrogen peroxide solution is made from elemental hydrogen and oxygen for catalytic action, and then reacts with olefins to form epoxidized olefins in the liquid phase epoxidation in the presence of titanium banknotes , And the solvent was refluxed to the process. Propylene oxide is one of the most important basic chemicals in the chemical industry. Among the above applications, it is used in na types, especially in the preparation of polyscale and polyalcohol to synthesize polyaminomethyl pigment. In addition, propylene oxide derivatives also account for a relatively large portion of the market in the field of ethylene glycol, especially lubricants and antifreeze agents. The preparation of essentially epoxidized olefins is known. Olefins are used as initiators and are oxidized by very wide variations. However, for economic reasons, it is better to use hydrogen peroxide or air. Titanium ore-catalyzed epoxidation is possible using pure oxygen as an oxidant in the presence of a redox system including alkylanthrahydroquinone and alkylenquinone (US 5 221 795). The disadvantage of this reaction is the continuous loss of a small amount of anthraquinone and organic solvents, which is the result of the oxidative decomposition of their organic compounds. When using a platinum metal-containing titanium banknote ore and a gas mixture including molecular oxygen and molecular hydrogen (WO-97 / 47 386, WO-96 / 023 023), the yield of propylene oxidation may be very low (about 1 to 2%) and unsatisfactory selectivity from 60 to 70% of propylene oxide. Secondary reactions of hydrogenation will result in the generation of large amounts of propane by-products. U.S. Patent Nos. 5 623 090 and WO-98 / 00 413-15 disclose that in the presence of gas, propidium is directly oxidized to propylene oxide with molecular oxygen. A commercially available titanium dioxide system containing extremely dispersed gold particles is used as a catalyst. (Please read the note on the back 3 to write this page) Write too

The paper & degree applies the Chinese National Standard (CNS) A4 specification (210x297 mm) 1232860 ^; ^ Printed by the Consumers ’Cooperative of the Bitter Intellectual Property Bureau A7 V. Description of the invention (2) Except for the low output, both methods have A very expensive disadvantage is that the catalyst contains gold. Therefore, for economic benefits, it is absolutely necessary to continue to develop catalyst systems with excellent catalytic activity and improved usability. U.S. Patent No. 4 833 260 teaches that the use of an oxidizing agent, nitrogen peroxide, in the liquid phase, the titanium mirabilite catalyst can effectively perform the epoxidation of dilute hydrocarbons. In the case of Miao Mine, 'Yes-a small part of the Shi Xi lattice is replaced by titanium (US 4 410 50D. However,' H 2 O 2 is so expensive that it cannot be used in large quantities until now. In the use of hydrogen peroxide Most of the increased cost is caused by hydrogen peroxide itself, because the concentration of hydrogen and oxygen in the preparation must be observed very closely as a safety measure. The reaction solution containing the low-concentration secret is mainly obtained and then must be performed. High-cost condensation, purification and stabilization. The production of hydrogen peroxide is in principle the latest technology known for this purpose. It has long been known that hydrogen peroxide can also be produced directly from elemental hydrogen and oxygen using suitable catalysts. Its It has also been known for a long time that mixtures of gaseous oxygen and hydrogen produce explosive gas mixtures. Therefore, all industrial H2O2 methods indirectly combine hydrogen and oxygen. Over 90% of hydrogen peroxide products in the world are currently imported by the method of anthraquinone Among them, the alkyl anthraquinone series is typically used as a chemical auxiliary substance. The disadvantage of this reaction is that as a result of the thermal decomposition and oxidation of their organic compounds, the lyon quinone Loss of organic solvents and high cost of extraction, purification and distillation steps. The direct synthesis of elemental hydrogen and oxygen is a goal of unremitting research, but it has not yet entered any commercial application. In addition to safety issues, the most important issue is to avoid The formed hydrogen peroxide is then decomposed into water and oxygen. This problem can be | installed ------- order, Ί, ------- (Please read the note on the back 2 items to write this page}

This paper size applies the Chinese national standard (cns) A4 specification (210 x 297 public love) 1232860 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (3) Solved by continuous operation at high flow rates. However, as a result, when the reaction rate is low, the concentration of hydrogen peroxide contained in the emissions is too low to make the method incompatible with the benefit. For those who use 1 bar catalyst to form hydrogen and oxygen to form hydrogen peroxide, US 4_252 reveals that the most appropriate ratio of radon to radon is from 15:】, that is, within the explosion range. The transition metals of subgroup 8 are particularly the most heterogeneous species as catalytically active species. Precious metals can hide on various supports such as Ti () 2, scratch, Al203, Teflon, catalyst monolith made of activated carbon or woven fiber, such as' V4a, with activated carbon being the most commonly used. Methods based on these catalyst systems have been patented by many companies and agencies such as U.S. 4,279,883, U.S. 4,661,337 EP-117 306, and DE-196 42 770. US 4 336 238 and US 4 336 239 describe the reaction of using a palladium-containing catalyst in an organic solvent or a solvent mixture, and optionally containing water to form hydrogen and oxygen into hydrogen peroxide. The concentration of hydrogen peroxide obtained with a reaction gas mixture having a hydrogen content of less than 5% by volume is at most 2.4% by weight, which is too low for economic benefits. In addition, after 285 hours of operation, the catalyst activity dropped to 69% of its original value, which is still too low for industrial use. Special solid supports for spray-dried colloidal stone gum are described in U.S. 5 352 645 and WO-92 / 04 976. EP-627 381 discloses the use of niobium, and the molybdenum and iron oxides are the supporting substances, which can be distinguished by high acid resistance. However, in the mentioned specification, hydrogen peroxide is often prepared by a batch or semi-continuous method, which is very unsuitable for industrial use. In addition, the reaction time is too short to obtain the end of the catalyst life (please read the notes on the back first to write this page).

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i. Description of the invention A method for preparing an epoxidized olefin in the presence of a zeolite containing synthetic titanium atoms in the range of (5) to 0.04, characterized in that the method includes the following steps, a) by a continuous reaction of hydrogen and oxygen, A dilute hydrogen peroxide solution of an alcohol or an aqueous alcohol is prepared by using a catalyst mainly containing a subgroup 8 element as an active component, wherein those solutions optionally further include a stabilizer, b) a selective passivation stabilizer, c) an olefin and The alcohol or aqueous alcohol is diluted with a hydrogen peroxide solution for reaction, d) the epoxidized dilute hydrocarbons are separated, e) the stabilizer contained in the alcohol or the water-containing diluted hydrogen peroxide solution is selectively released, The dilute hydrogen peroxide solution of the alcohol or water-containing alcohol is refluxed to process a), wherein the dilute hydrogen peroxide solution of the alcohol or water-containing alcohol is not separated between individual subsidiary steps. The method according to the invention is applicable to all olefins. Preferred for unsaturated hydrocarbons ranging from 1 to 12 carbon atoms, especially ethylene, propylene, butene, 2-butene, butadiene, pentene, hexene, isoprene , Rare and cyclohexene. The dilute hydrogen peroxide solution of alcohol or water-containing alcohols printed by employees of the Intellectual Property Office of the Ministry of Economic Affairs usually has a content of 102 from 0.5 to 12% by weight, especially from 2 to 7% by weight. When preparing hydrogen peroxide, a suitable reaction medium is an alcohol or water or a mixture thereof. Suitable alcohols are all alcohols known to those skilled in the art, such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol 'heptanol and octanol. Of course, their alcohols can also be branched. For example, 61232860 A7, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and the invention description (for example, isobutanol, second-butanol, and 箆-夂 弟 二 · Butanol. Methanol is more zoxanol. Of course, it can also be demineralized ^^ Shellfish: ¾ retorted water. Hydrogen peroxide should be carried out in an overflow reactor. Σ formation of a suitable catalyst system has been Known for the continuous reaction of nitrogen and oxygen which is good at solving this problem, and it can be converted into hydrogen peroxide. It is better to use the catalyst system which contains the main subgroup 8 elements, especially as Component. The catalyst should be the catalyst type of the molded body. The catalyst of the catalyst is the active catalytic component of the catalyst on the surface of the support. Specially shaped support, such as Leixu's ring coffee Iron (Sattei) body, wire spiral tube or wire mesh ring. Additional examples can be found in Rompp-Chemie-Lexikon, ninth edition, 1453ff. And the use of catalyst monoliths is preferred. Catalyst monoliths are usually Made of woven fibers, knitted fibers, films, It is made of expanded metal and / or metal plate. Open-cell type, for example, polyaminomethyl ester, ceramic or melamine resin type is also suitable. Active catalyst components are applied to their catalyst monoliths In order to increase the catalytic activity, the catalyst may optionally contain other metal additives, for example, platinum, money, rhenium, steel, silver and / or gold. The ratio of Mingba to additives is from 100 to 1 to 1 to 10. Within the range, especially from 10 to 1 to 1 to 1. The content of palladium and additives is usually from 5.10 to 4 to 1% by weight, especially from 103 to 0. 5% by weight. For details, please refer to DE-196 42 770, which discloses a preferred method for preparing dilute rhenium peroxide solutions of alcohols or aqueous alcohols. However, DE-26 15 625, DE-26 55 920; US 4279 883, US 4661 337, US 4336 239 ， US 4379 778; ^ The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 χ 297 mm)-installed—— (Please read the precautions on the back first ^^^-write this page) — J — · -ϋ nn ϋ ·

1232860 Printed A7 by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (7) US 4 389 390, EP-1 17 306, US 4889 705, US 4681 751, US 4772 5458, US 4240 933, US 4832 938, The methods disclosed in WO-92 / 04 277, US 5169 618, EP-579 1109, Ep 623 552 and WO-96 / 0538 are also suitable. Dilute hydrogen peroxide solutions of alcohols or aqueous alcohols usually contain stabilizers to avoid decomposition of the hydrogen peroxide formed. The stabilizer is usually an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, and hydrochloric acid and sulfuric acid are preferred. It is usually used in an amount ranging from 104 to 101 mol / liter, preferably from 5 to 25 · 10-3 mol / liter. Other stabilizers are optionally present, for example, they are in US 4 889 705 and US 4 681 751. Particularly advantageous are salts, e.g., qualitative desert compounds' qualitative chlorides, qualitative phosphates and alkaline sulfates, more particularly sodium chloride, sodium desertification, potassium chloride and desertification. It is usually used in an amount ranging from 0.5 to H) millimolars / liter, preferably from 5 to 2 millimolars / liter. &amp; Although the amount of acid added was stated to be beneficial for stabilizing the peroxide gas, the basin could cause the selectivity of the epoxidized dilute hydrocarbons corresponding to the epoxidation performed in the second stage to be drastically reduced. In the presence of an acid and water, the formed epoxides are hydrolyzed to the corresponding glycols and oligomers. For this reason, the acid and desert ion concentrations must be kept very low (acid content <0.5% by weight). In the complete method according to the present invention, the dilute hydrogen peroxide solution system before reacting with dilute hydrocarbons can therefore be used to conveniently make Qiu neutral, weakly acidic, or weakly tested ^ from 4 to 9, especially from 5 to 8, more particularly a pH value from .5 to 7.5 is preferred. It should be appropriate to use the appropriate ion exchanger to reach "· I I I I I J I- · Ί 1 — — — — — —-f Please read the notes on the back first, write this page} |

This paper size applies the Chinese National Standard (cks) A4 specification (21〇_297 mm) 1232860 A7 B7 V. Description of the invention (8), but other methods are known to those skilled in this area to neutralize Dilute hydrogen peroxide solution is also appropriate. Suitable ion exchangers include, for example, crosslinked polymers. These supporting substances can be used in a wide variety of ways in multi-catalyst organic reactions. Flexibility for structural and functional changes allows all catalytically active components to be physically fixed. Strong acid polymers, for example, their functionalized groups with sulfonic acids can often be replaced by inorganic acids in catalytic reactions. These acidic polymers can be reversibly converted into the form of a neutral base using a base. The ion exchangers described in Ullmann, Encyclopedia of Industrial Chemistry, 5th edition (1989), AU, pages 393 to 411 are also suitable. Surprisingly, if a dilute hydrogen peroxide solution containing an inorganic acid is partially or completely neutralized with a cation exchanger as described before reaction with an olefin,> 85% fixed propylene oxidation can be achieved物 Selectivity. The reaction of the olefin with the alcohol or a dilute hydrogen peroxide solution of the aqueous alcohol is preferably carried out by the method described in EP-A1 -100 119. In this method, the epoxy / dolefin is a dilute hydrogen peroxide solution of an olefin and an alcohol or a water-containing alcohol, and has a general formula of xTi〇2 ((1-x) Si〇2, where x is from 0.00%. Obtained in the presence of synthetic titanium zeolites in the range of 001 to 004. The article specifically mentions the use of 200 260, EP-A 230, 949, DE-A1-196 23 608, and 196 23 611 to improve the method. Of course, it is also possible to use other methods in the complete method of the present invention by diluting smoke with a dilute hydrogen peroxide solution of the alcohol or aqueous alcohol, in the general formula xTi〇2 · (1_χ)

SiO2, where X is from Q. to U4 in the presence of synthetic ^ stone in the presence of epoxidized olefins. (Please read the notes on the back first

丨 J Pack ------- r It Order 1 '------- Write this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -10-1232860 A7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs System V. Description of the invention (9) It is also advantageous to replace some or all of the titanium atoms with a europium atom. It is also advantageous to neutralize the acid surface portion of the zeolite containing synthetic titanium atoms in the general form xTi〇2 • (Bux) Si〇2, where χ is from 0.00 to Wang υ 04. The epoxidized olefins formed are separated by conventional methods, such as decantation, and optionally under reduced pressure. For the formation of Η202, the reaction medium must be as multi-protonic as possible and for oxidation, it must be as filamentous as possible. On the reflux of the oxidizing gas solution: With today's content: = hydrogen oxide, using this method to prepare a dilute hydrogen peroxide solution of alcohol or aqueous alcohol, which may be advantageous after the propylene oxide is separated, and the inactive Or the neutralized stabilizer is released again. The effect of adding or passing the consumed hydrogen peroxide solution through the corresponding ion exchanger is advantageous. By selectively changing the reaction parameters, it is particularly advantageous to regenerate the previously used cation exchanger. Of course, at this stage, additional stabilizers may be added or replaced with depleted or lost stabilizers. Suitable ion exchangers are organic and / or inorganic polymers, for example, by the sulfonic acid group (e.g., from Bayer AG, D ion exchangers (e.g., Lewatit®, Bayer catalyst ⑧K113) or £ 2431) or functionalized from Rohm and Haas, USA (eg, Amberlist® 36W, Amberlist® 3 WET, Duolite® ARC 9652)).离子 The ion exchangers described in the Herman Encyclopedia of Industrial Chemistry, 5th edition (1989), pages A14, 393 to 411 are also suitable. Finally, the consumed hydrogen peroxide solution is refluxed back into the alcohol or aqueous alcohol-containing dilute hydrogen peroxide solution (step a)). Note t order

-11-This paper is suitable for Chinese National Standard (CNS) A4 specifications (210 X 297 public love) 1232860 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (11) Examples of corruption 1 Preparation of a catalyst The catalyst monolith of the support woven fiber V4A is similar to DE196 42 770 A1. A cylindrical V4A monolith is composed of a wavy and smooth V4A mesh (substance: 1.457 liters; mesh size: 200 microns; wire diameter : 150 microns). The monolithic support is free from fat by conventional methods. It is dissolved in 80 ml of distilled water using solvent; 5 ml of 10 / 〇 [Pd (NH3) 4] (NO) 3) 2 solution is added at 80 °. It was stirred at C for 24 hours. The monolith was separated from the liquid phase, washed 4 times with 100 ml of demineralized water each time, dried at 110 ° C for 2 hours and then reduced under nitrogen at 200 ° C for 2 hours (combined by amine Thermal decomposition of materials and automatic reduction of ammonia). Example 2 a) Preparation of hydrogen peroxide The monolithic Pd catalyst of Example 1 was placed in a 400 ml V4A stirring autoclave with a gas stirrer, the temperature was controlled by a heat conductor, the pressure was maintained at 70 bar, and a central data detection system The middle is about the center of the stirring shaft. The supply lines for hydrogen, oxygen and the reaction medium are located on the base of the reactor. A tube in the reactor cover continuously removes the liquid / gaseous mixture. 0.3% by weight of acetic acid, 0.03% by weight of filled acid and 5 ppm of bromide (in the form of sodium desert) were added to a reaction medium including methanol. The reaction medium was passed through the reactor at a constant pressure of 20 bar at a volume flow rate of 100 g / h and a constant flow of nitrogen at 60 liters / h. At the beginning of the reaction, the flow of oxygen and hydrogen at the same volume ratio of 92: 8 volume ratio replaced the nitrogen stream. -13-(Please read the notes on the back first

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-Ί II »1-This paper &amp; degree applies to China National Standard (CNS) A4 (210 X 297 mm) 1232860 Printed by the Consumers’ Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (1 2) The methanol / water solution has a hydrogen peroxide concentration of from 2 to 6% by weight of hydrogen peroxide. The solution obtained from 2a) was used directly in Example 2b). b) Example 2a) H2S〇4 / H3P〇4 / H2 02-methanol solution neutralization before ion exchanger treatment · 100 * Lewatit S 100 (Bayer) was stirred in 300 g of 10% NaOH for 2 hours , Then filtered and washed with a total of 1.5 liters of water until the washing solution showed a neutral pH. In each case, the nano-type cation exchanger was stirred 3 times in 100 g of methanol for 30 minutes each to exchange water-methanol. The pre-treated ion exchanger and 100 g of methanol were transferred to a monolayer adsorption column (3 cm in diameter and 30 cm in length; Lewatit packed at 12 cm in height). 251 g of H2S04 / H3P04 / H2 02-methanol solution was passed through the pre-treated ion exchanger in a time course of 50 minutes and then rinsed with 150 ml of methanol, and the eluate was collected into 10 parts each About 50 ml. The contents of the precipitates and in each part were determined by the titration method. The hydrogen peroxide completely left in the chromatographic separation adsorption column, that is, no decomposition. The sulfuric acid and phosphoric acid contained in it are from about 75 to 85% and can be neutralized by flowing through the cylinder once (Figure 1). Acid titration method: Weigh about 10 grams of sample, add water to make about 150 ml, and add 5 drops of 1% phenolphthalein solution, then titrate with 0. in NaOH (0.4 g / L) (blank value <1 drop) . H2O2 titration: 60 ml of sulfuric acid (1 mole / liter) was added to 1 g of sample; water was added to make the mixture 170 ml and titrated at 0.1 μm KMη04 (3.16 g / liter) (blank value) &lt; 1 drop). The solution of Example 2b) was used directly in Example 2c). ί 装----— J—-Order’1! ------- (Please read the note on the back? Matters write this page} -aB »i

14-1232860 A7 B7 V. Description of the invention (1 3) c) Preparation of propylene oxide in a 1 liter stirrer autoclave with magnet, water and thermocouple control the temperature and the supply official in the reactor base can be fresh It is prepared to partially neutralize the hydrogen peroxide (from about 3 to 5%) from 2b) and for gaseous propylene. In a typical manufacturing method, 500 grams of a dilute hydrogen peroxide solution is placed in a 45 C nitrogen-filled reactor, and 2 grams of a synthetic titanium wonderful expansion system with a content of 2.8% titanium, such as EP-A1-100. Suspended as described in 119, and gaseous propylene was metered in and stirred vigorously to a pressure of 4 bar. During the reaction, propylene was further metered in; thus the pressure of 4 bar was kept constant. Under these conditions, the effect of oxidation to propylene oxide is very fast and optional. After 70 minutes, more than 95% of the hydrogen peroxide was consumed and propylene oxides with selectivity from 85 to 92% were found (Figure 1). d) Free the stabilizer obtained from 2b) After removing the propylene oxide by steaming the crane, pass the solution obtained from 2C) through the chromatographic adsorption column used in 2b) in the opposite direction. The neutralized acid is reconverted to the acid form to a degree of more than 70 to 80%. Its pH value is &lt; 1. (Please read the note on the back-peak loading item before filling in I-I 嫌 一 ί I I I I I, this page)

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Claims (1)

1232860 A8 B8 C8 D8 VI. Scope of patent application ^ Patent Application No. 88120936 ROC Patent Appln. No. 88120936 The application for a positive application I Liweiwei Chinese appendix (1) Amended Claims in Chinese — Enel. I (^ 1791 year 5 (Presented by y / ajii) (Submitted on May 2002) 1. A dilute hydrogen peroxide solution of olefins and alcohols or aqueous alcohols in the general formula xTi〇2 · (1-x) Si〇2 where X is from A method for preparing an epoxidized olefin in the presence of a synthetic titanium atom-containing zeolite in the range of 0.001 to 0.004, which is characterized in that the method includes the following steps: a) by a continuous reaction of hydrogen and oxygen, mainly comprising subgroup 8 Elements as active components of catalysts to prepare dilute hydrogen peroxide solutions of alcohols or aqueous alcohols' where their solutions additionally contain stabilizers, b) the stabilizer is deactivated with the assistance of an ion exchanger, c) the olefin is reacted with the Alcohol or a dilute hydrogen peroxide solution of an aqueous alcohol is reacted, d) the epoxidized dilute hydrocarbon is separated, e) the stabilizer contained in the dilute hydrogen peroxide solution of the alcohol or the aqueous alcohol is selectively released, and A alcohol or dilute peroxy alcohol The nitrogen solution is refluxed to the preparation process a), wherein the alcohol or the water-containing alcohol dilute hydrogen peroxide solution is not separated between the individual subsidiary steps. 2. The method according to item 丄 of the scope of patent application, wherein or palladium-metal mixture is used as a catalyst in step ^. 3. The method according to item ⑻ of the scope of patent application, wherein the solution in step ^ contains an inorganic acid as a stabilizer. ------- 丨 丨 丨 丨 --t (Please read the notes on the back before filling this page) Order --------- line Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -16- 90. 11. 2,000! 23286〇